KR950003543B1 - Shell pound producing method for water clarification - Google Patents

Abstract

The shell powder is prepd. by i) washing, drying and pulverizing shell, ii) separating the obtd. shell powder with a sieze to obtain the 40-150 mesh powder, iii) processing the surface of the obtd. powder by boiling with an organic soln, and reacting with an inorganic acid soln. to obtain the porous shell powder, iv) neutralizing and stabilizing the porous shell powder with an alkali soln., washing and drying to obtain the final product. The obtd. shell powder is useful for clarificating agent of water.

Description

Shell Shell Production Method

The present invention relates to a method for producing shell shell powder. More specifically, the present invention relates to a method for preparing shell shells by surface treatment with an organic solvent, an acid, and a base using shells for disposal as raw materials.

Shell shell produced by the present invention can exhibit an excellent effect to purify heavy metals, toxic residual pesticides, various organic harmful substances, detergents, etc. contained in waste water, drinking water, water supply and the like.

About shell, specialty magazine {K. Nagasawa and H. Watanabe, J. Chromatogr., 47, 408 (1970)}, which can be used as fillers, and also in the magazine {i) G.Mckay, HSBlair and JRGardner, J.Appl.Polymer. Sci., 27, 3043-3057 (1982), ii) G. Mckay, HSBlair and JR, Gardner, J. Appl. Polymer Sci., 29, 1499-1514 (1984)}. have.

In addition, charcoal, zeolite, bentonite, and the like have been commonly used for purification, but these depend on imports, and most of them are economically difficult because they are expensive.

The present inventors use the shells obtained by processing and manufacturing the shells disposed of with organic solvents, acids, and bases in wastewater, drinking water, and water sources heavily contaminated with industrial wastewater and domestic wastewater, and heavy metals contained in them and toxic pesticides. The present invention has been found to have excellent effects in purifying various organic harmful substances, detergents, and the like.

Accordingly, it is an object of the present invention to provide a method for producing shell shells which can exhibit excellent effects in purifying heavy metals, residual pesticides, organic harmful substances, detergents, etc. contained in waste water, drinking water, water supply, and the like.

Hereinafter, the present invention will be described in detail.

The present invention is a method for producing shell shells in which shells are added with an organic solvent, an inorganic acid and a base in order to react, washed with water, filtered, and dried to stabilize the shells.

Referring to the present invention in more detail as follows.

According to the present invention, as a shell, for example, stalk, ramie, mussels, oysters and flavored clams are mainly used, and in use, the shells are collected, washed and dried first, pulverized, and then used as a standard sieve. Filter out the particle size. The standard network can be used in the size of 40, 50, 60, 70, 100, 150 mesh.

In the present invention, the shells selected as described above are subjected to surface treatment with an organic solvent, an acid, and a base. The reason is that the main chemical composition of the shell is CaCO ₃ , and CaCO ₃ is contained in minerals (marble, limestone, etc.). CaCO ₃ in shell is different from mineral CaCO ₃ because it contains about 5% of chitin and chitosan. This is because a complex compound is formed between CaCO ₃ and chitin, thereby increasing the adsorption effect (adsorption capacity).

In the present invention, for example, alcohols such as methyl alcohol and ethyl alcohol, ketones or ethers such as methyl ethyl ketone and acetone may be used as the organic solvent, and the selection may vary depending on the type of shell.

As the acid, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or perchloric acid in an aqueous solution of 1 to 10% may be used.

Meanwhile, as the base of the present invention, sodium hydroxide, potassium hydroxide, ammonium hydroxide and calcium hydroxide in 1 to 10% aqueous solution may be used.

Therefore, in the process of preparing shell shell according to the present invention, the selected shell shell obtained as described above is first surface-treated with an organic solvent, and then reflux-cooled at a boiling point of the solvent for about 12 to 24 hours for extraction of the organic substance. Drying at about 30 ° to 60 ° C. The shell powder processed with the organic solvent may then be porous with an inorganic acid and then neutralized with a base.

After the process using the organic solvent, acid and base for shell meal as described above, washed several times with water in a conventional manner, dried and stabilized to obtain the shell shell desired in the present invention.

Shell shell according to the present invention obtained in this way is heavy metals, toxic residue pesticides, etc. contained in wastewater, drinking water, water supply, etc. under serious conditions that contaminate human water as well as natural pollution due to the recent increase in industrial wastewater, domestic wastewater, It shows an excellent effect in removing various organic harmful substances, detergents and the like.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on an Example.

Example 1

Washing, drying and pulverizing the cornea shell, sifting the particles (40, 50, 60, 70, 100, 150 mesh) with a standard mesh and taking 500g of the cornea shell, and cooling the reflux with 1000 ml of 80% ethyl alcohol for 24 hours to remove the organics The surface was extracted and processed, and dried at 60 ° C. for 2 hours.

The dried shell shell was treated with 1000 ml of 5% hydrochloric acid to make a porous surface, and then the reaction was stopped by treating it twice with 500 ml of 5% sodium hydroxide, washed three times with water, and dried to obtain 410 g of stable shell shell shell. .

Example 2

Washing, drying and pulverizing the clam shell, washing the particles with a standard mesh as in Example 1, taking 500 g of clam shell shell, extracting the organics while reflux cooling with 1000 ml of 60% methyl alcohol for 24 hours and surface Was processed and dried at 60 ° C. for 2 hours.

The dried shell meal was treated twice with 800 ml of 3% perchloric acid to make the surface porous, and this was neutralized twice with 500 ml of 3% potassium hydroxide, washed three times with water, and dried to obtain 400 g of stable shellfish shells.

Example 3

The mussel shells were washed with water, dried and pulverized, and 500 g of mussel shells were taken by screening particles with a standard mesh as in Example 1, and the organics were extracted while refluxing with 1000 ml of 60% methyl ethyl ketone for 12 hours, and 40 It was dried for 2 hours at ℃.

The dried shell meal was treated with 1000 ml of 5% phosphoric acid to make the surface porous, which was neutralized twice with 500 ml of 3% calcium hydroxide, washed three times with water, stabilized by drying, and 400 g of mussel shell meal was obtained.

Example 4

The oyster shells were immersed in water for 24 hours, washed, dried and pulverized, and 500 g of oyster shells were taken by screening particles with a standard mesh as in Example 1, and the mixture was refluxed with 1000 ml of ethyl ether for 24 hours Lipids were extracted and dried at 30 ° C. for 3 hours.

The dried shell meal was treated with 500 ml of 3% sulfuric acid to make the surface porous, neutralized three times with 500 ml of 3% ammonium hydroxide, washed three times with water, and stabilized by drying, to obtain 390 g of oyster shell meal.

Example 5

The clam shells were washed with water, dried and pulverized, and the particles were sorted with a standard mesh as in Example 1 to take 500 g of clam shell shells, which were extracted with reflux cooling with 1000 ml of acetone for 12 hours, followed by 2 hours at 40 ° C. Dried over.

The dried shell meal was treated twice with 500 ml of 3% nitric acid to make the surface porous, and this was neutralized twice with 500 ml of 3% sodium hydroxide, washed three times with water, and dried to obtain 420 g of stable shell shell shell.

[Heavy metal adsorption experiment using shell meal]

As heavy metal reagent, 50 ml of heavy metal solution containing 1 ppm, 10 ppm, 100 ppm and 250 ppm of heavy metal Pb, Cd, Cu and Ag were prepared using Pb (NO ₃ ) ₂ , Cd (NO ₃ ) ₂ , CuCl ₂ and AgCl. The solution was added to a flask containing 2 g of the keratoshell shell prepared in Example 1, stirred for 2 hours, filtered, and the filtrate was analyzed by far ultraviolet spectrum. The results are shown in Table 1 below.

TABLE 1

[Adsorption of Toxic Pesticides Using Shell Flours]

Pesticides that are highly toxic in pesticides are organochlorine, γ-BHC, Endrin, pp'-DDT, and organophosphates Diazinon, Parathion, EPN and carbamate, Cabaryl 50 ml of the mixed solution containing the same amount (ppm) as in Table 2 was added to 2 g of shellfish shells prepared in Example 2, stirred for 2 hours, 4 hours, and 6 hours, respectively, and filtered. The filtrate was extracted with hexane-ethyl acetate (1: 1) solution and analyzed by gas chromatography. Residual pesticide adsorption amount by the extraction time is shown in Table 2 below.

And, as shown in Table 3, the adsorption amounts for the first sample, the second sample, and the third sample whose initial doses of the pesticide components are changed are shown in Table 3 below.

TABLE 2

TABLE 3

[Adsorption Experiment of Trihalomethane Using Shell Flour]

50 g of a mixed solution of bromoform, chloroform, and chlorodibromomethane in 2 g of the mussel shell powder prepared in Example 3 was divided into a first sample, a second sample, and a third sample as shown in Table 4 below. After stirring for 2 hours with change, the filtrate was extracted with pentane. The results of analyzing the extract by gas chromatography are shown in Table 4 below.

TABLE 4

Note) THMS: Trihalomethane

[Adsorption Experiment of Surfactant Using Shell Flour]

50 g of sodium dodecylbenzene sulfonate solution was added to 2 g of the oyster shell powder prepared in Example 4 while stirring for 2 hours while changing the concentration (first sample, second sample and third sample), as shown in Table 5 below. After filtration, the filtrate was aliquoted and analyzed using spectrophotometry (methylene blue method). The results are shown in Table 5 below.

TABLE 5

[Phosphate Adsorption Experiment Using Shell Flour]

50 g of phosphate solution was added to 2 g of the shellfish shell prepared in Example 5 while stirring and filtering for 2 hours while changing the concentration (first sample, second sample, and third sample) as shown in the following Table 6. The solution was analyzed by ion chromatography. The results are shown in Table 6 below. In addition, the result of measuring the COD by aliquoting the solution is shown in Table 7 below.

TABLE 6

TABLE 7

[Cleaning method using shell meal]

After filling the shell layer (about 8 cm) prepared in Examples 1 to 5 to the tube (40 cm, ø2.2 cm), 10 ml of solution containing 10 ppm of Pb, 10 ppm of Cu, 10 ppm of phosphate, and 10 ppm of surfactant was added. After passing through the tube filled with shell powder, the filtrate was analyzed. The analysis results are shown in Table 8.

TABLE 8

SDS: Sodium Dodecylbenzene Sulfonate

As can be seen from the above experimental results, the shell meal of the present invention uses the adsorption capacity of the shell, which is a waste resource, and efficiently removes heavy metals, toxic pesticides, organic harmful substances, detergents, etc. from wastewater, drinking water, and drinking water at very low cost. There is an effect that can be purified.

Claims (10)

The shells were washed with water, dried and pulverized, and then screened with particles of 40 to 150 mesh using a standard network, and the selected shells were refluxed at a boiling point of the organic solvent in an organic solvent to extract organic substances in the shells. A shell powder for purification of water, wherein the shell powder surface-treated with a solvent is porous with an aqueous inorganic acid solution, and then neutralized and stabilized with a basic aqueous solution, washed with water, and then dried. The shell meal according to claim 1, wherein the shell is selected from the group consisting of scapula, ramie shells, mussels, oysters and flavor shells. The shell meal according to claim 1, wherein the organic solvent is one selected from the group consisting of methyl alcohol, ethyl alcohol, methyl ethyl ketone, acetone and ethyl ether. The shell meal according to claim 1, wherein the inorganic acid aqueous solution is selected from the group consisting of 3 to 5% hydrochloric acid, perchloric acid, nitric acid, sulfuric acid, and phosphoric acid aqueous solution. The shell meal according to claim 1, wherein the shell solution is selected from the group consisting of 3-5% sodium hydroxide, potassium hydroxide, and ammonium hydroxide aqueous solution. The shells were washed with water, dried and pulverized, and then screened with particles of 40-150 mesh using a standard network, and the selected shells were refluxed at 12-24 hours at the boiling point of the organic solvent in an organic solvent to recover the organic matter in the shell. After extraction, the shells surface-treated with an organic solvent were made porous with an aqueous inorganic acid solution, and then neutralized with a basic aqueous solution two to three times, and then the surface reaction was stopped.Then, the mixture was washed three times with water, and then 30 ° to 60 °. Method of producing a shell powder stabilized by drying for 2 to 3 hours at ℃. The method for producing shell shell according to claim 6, wherein the shell is selected from the group consisting of stalk, ramie, mussel, oyster and flavored shell. The method for producing shell shell according to claim 6, wherein the organic solvent is one selected from the group consisting of methyl alcohol, ethyl alcohol, methyl ethyl ketone, acetone and ethyl ether. The method for producing shell shell according to claim 6, wherein the inorganic acid aqueous solution is selected from the group consisting of 3 to 5% hydrochloric acid, perchloric acid, nitric acid, sulfuric acid, and phosphoric acid aqueous solution. The method for producing shell shell according to claim 6, wherein the base aqueous solution is selected from the group consisting of 3-5% sodium hydroxide, potassium hydroxide and ammonium hydroxide aqueous solution.